US2846417A - Terpolymers of nu-acrylamidoalkyl betaines - Google Patents

Terpolymers of nu-acrylamidoalkyl betaines Download PDF

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US2846417A
US2846417A US415161A US41516154A US2846417A US 2846417 A US2846417 A US 2846417A US 415161 A US415161 A US 415161A US 41516154 A US41516154 A US 41516154A US 2846417 A US2846417 A US 2846417A
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parts
water
copolymer
betaine
dimethyl
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Shacklett Comer Drake
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EIDP Inc
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EI Du Pont de Nemours and Co
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Priority to BE535582D priority patent/BE535582A/xx
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Priority to US415161A priority patent/US2846417A/en
Priority to GB32913/54A priority patent/GB786345A/en
Priority to FR1122084D priority patent/FR1122084A/fr
Priority to DEP13535A priority patent/DE1046318B/de
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/04—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with macromolecular additives; with layer-forming substances
    • G03C1/053—Polymers obtained by reactions involving only carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/52—Amides or imides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S260/00—Chemistry of carbon compounds
    • Y10S260/15—Antistatic agents not otherwise provided for
    • Y10S260/17—High polymeric, resinous, antistatic agents

Definitions

  • This invention relates to organic addition polymers and to their preparation. More particularly, it relates to addition polymers of high molecular weight which contain unsubstituted or alkyl-substituted extralinear amide groups, dihydroxyalkane-substituted extralinear amide groups, and betaine-substituted extralinearamide groups. Still more particularly, it relates to such copolymers which have peptizing, dispersing, and protective colloid properties.
  • Gelatin has been widely used as the water-permeable colloid binding agent for the light-sensitive silver halide grains in photographic dispersions or emulsions. It has ties, in addition to its excellent protective colloid properties. Gelatin has a number of disadvantages, however, being subject to attack by bacteria and molds and lacking uniformity. It has extremely variable properties which depend upon its source and the particular treatments which have been applied to it.
  • Various natural and synthetic colloids have been proposed as substitutes for gelatin. The natural materials, in general, are inferior to gelatin. The proposed synthetic materials, while possessing reasonably useful protective colloid properties and forming freely water-permeable films, are not as satisfactory as gelatin as dispersing and protective colloid agents. By using such synthetic colloids it has not'been possible to make photographic silver halide emulsions of the high sensitivity to light required for negative and X-ray emulsions.
  • An object of this invention is to provide a new class of organic copolymers of high molecular weight. Another object is 'to provide such copolymers which are useful as water-permeable colloids. Still another object is to provide such copolymers which possess the advantageous properties of gelatin but are free from its disadvantageous properties. A further object is to provide synthetic polymers which are useful as gelatin substitutes and permit the manufacture of high speed negative and X-ray type photographic silver halide emulsions. A still further object is to provide organic copolymers which can be gelled, de-gelled and re-gelled and form firm, strong, water-permeable, thin layers. Still other objects will be apparent from the following and more detailed description of the invention.
  • R is a member'taken from the group consisting of hydrogen, alkyl of 1 to 3 carbon atoms, phenyl and cyclohexyl
  • Q and Q are members taken from the group consisting of hydrogen and alkyl of 1 to 3 carbon atoms
  • m is 0, 1, 2, 3, or 4
  • n is O'or 1 and the sum of m and It must equal at least 1;
  • R is a member taken from the group consisting of hydrogen, alkyl radicals of 1 to 3 carbon atoms, phenyl and cyclohexyl, R is a saturated bivalent aliphatic hydrocarbon radical of 2 to 6 carbon atoms, R is an alkyl radical of l to 3 carbon atoms, 113113.311 alkyl radical of 1 to 3 carbon atoms, and R is a saturated bivalent aliphatic hydrocarbon radical of 1 m4 carbon atoms; and
  • Rnlmeos/ I III wherein R, R and R'" are members taken from the group consisting of hydrogen, alkyl of 1 to 3 carbon atoms, phenyl and cyclohexyl.
  • These copolymers may contain'l, 2 or more different units of each of- Formulas, I, II, and III, as Will be apparent from the following general description and working examplesiof the preparation of the novel copolymers.
  • Suitable alkyl radicals comprehended by the above formulae include methyl, ethyl, propyl, and isopropyl. In the case of (CH- the useful radicals are methylene, bimethylene, trimethylene, and tetramethylene.
  • v I V The addition copolymers described in the.
  • acetals contemplated in 1(b) above are those which can be purified by distillation. Such acetals are those obtainable from carbonyl compounds of 1 to 7 carbon atoms and are described in Schacklett .U. S. application Serial No. 389,872, filed November 2, 1953.
  • the ester a dssrsatadilat d is 2(12) ab ve a ho which are obtainable from ct-halogenated esters and are described in U. S. application Ser. No. 389,873, filed Net emb -(U- 3- Paten 2 7 2 ran ed 1 he. re e t .(l).
  • the polymerization is carried out in a suitable solvent, e. g, water or mixtures of water with a watermiscible solvent, including methanol, ethanol, propanol, isopropyl alcohol, and tertiary butyl alcohol, and may be accelerated byheat, actinic lightzof wavelengths between 1800. and 7000A. .Uyand an addition polymerization initiator; or aicombination of these conditions.
  • Suitable initiators includexorganic .and inorganic peroxides, alkali metal. and ammonium persulfates, azonitriles and amamidinehydrochlorides.
  • the polymerization preferably is'carried outbetweenAOC. and70 C. since polymers of suitable molecular weight are obtained within this range. At higher temperatures there is a tendency for lower molecular weight polymers to be formed, and at lower temperatures higher molecular weight polymers are formed.
  • concentrations of monomers may be present inthe solvent medium and concentrations from /2 'to 2 molar are preferred. It has'been found that an increase in monomer concentration results in copolymers of higher molecular weight while a decrease in polymer concentration results in'copolymers of lower molecular Weight.
  • the resulting viscoussolution is treated with a water-miscible non-solvent for the polymer, e. g., acetone, methyl ethyl ketone, methanol, ethanol, or dioxane, which treatment precipitates the polymer in the form of a white solid which may be broken up, reduced or ground to smaller sizes, washed and dried.
  • a water-miscible non-solvent for the polymer e. acetone, methyl ethyl ketone, methanol, ethanol, or dioxane
  • eompoimds having Formula IV above
  • the amidation reaction is preferably carried out in the presence of aqueous alkali, e.
  • The' reactants (2) constitute the subject.
  • Suitable inert diluents include diethyl ether, acetone, methylethyl ketone, tetrahydrofuran and dioxane.
  • Suitable reactants (3) (having Formula VI) are well known and described in various chemical journals, textbooks and patents, and in the applications referred to above. Further, it is .to be understood that any of the reactants ((l), (2) and (3) above) Which are comprehended by the general formulae and are described in the applications referred to can be used in making the addi tion copolymers of this invention, having three or more components.
  • reactants contain hydrolyzable acetal groups or carboxylic ester groups as in reactants (l) and (2) above, these groups can be hydrolyzed prior to, during, or subsequent to, the addition polymerization reaction.
  • betaine derivatives reactant 2(b) they may be added to the copolymerization reaction zone in the unhydrolyzed form.
  • a suitable acid e. g., hydrochloric, sulfuric, phosphoric, or acetic, may be added to neutralize the base before precipitation of the copolymer.
  • acetal derivatives (reactant 1(b)), they likewise may be added to the copolymerization zone in unhydrolyzed form. In such case, it is preferable to hydrolyze the copolymers containing such acetal groups, before precipitation of the polymer with a water-miscible non-solvent therefor.
  • This hydrolysis may be accomplished by admixing with the solvent solution of the copolymer a snflicient quantity of a strong organic or inorganic acid, e. g., sulfuric,' hydrochloric, trichloroacetic, etc., to maintain its pH at about 2.0, for a period of one-quarter to one hour, at room temperature (25 C.).
  • a strong organic or inorganic acid e. g., sulfuric,' hydrochloric, trichloroacetic, etc.
  • a suitable'alkali e. g., 'so, dium carbonatefsodium hydroxide, ammonium hydroxide or potassium hydroxide may be added to neutralize the acid before preeipitationof the copolymer.
  • the polymerization initiator (referred to as initiator) is ,g'-azpbis(isobutyramidine hydrochloride) 3 and the relative viscosity is that of a 1% by weight aqueous solution.
  • the temperature was adjusted to 60 C., by means of a water bath, and nitrogen gas was passed through the water for a period of about /2 hour to remove dissolved oxygen. Then, 20.0 parts of N,4-methacrylamidometh-- yl-2,2-dimethyl-1,3-dioxolane, 22.8 parts of N,3-acrylamidopropyl-N,N-dimethyl-fl-aminopropionate betaine, 25.5 parts of methacrylamide, and 0.10 part of imtiator were added. The introduction of nitrogen was continued and I polymerization was allowed to proceed for 20 hours.
  • the copolymer solution was then adjusted to pH 1 to 2 for a period of about /2 hour and then neutralized to pH 7 as set forth in Example I.
  • Excess acetone was added to the copolymer solution, which treatment caused coagulation of the copolymer.
  • This substance. wasthen pulverized, and washed with acetone and dried to yield 58 partsof the white, water-soluble powder, namely, poly- (N,2,3 dihydroxypropoylmethacrylamide co N,3 acrylamidopropyl-N,N-dimethyl-,B-aminopropionate betaine co methacrylamide).
  • the relative viscosity of a 1% aqueous solution of this material at pH 7 and 30 C. was 1.75.
  • N,2-methacrylamidoethyl- N,N-dimethyl-fi-aminopropionate betaine a solution of 47.7 parts of N,2,3-dihydroxypropylmethacrylamide (prepared by hydrolysis of 59.8 parts of N,4-methacrylamidomethyl-2,2-dimethyl-1,3-dioxolane in 200 parts of water with dilute aqueous hydrochloric acid at pH 1 to '2 followed by neutralization with dilute aqueous NaOH to pH 7), 42.5 parts of methacrylamide, and 0.10 part of initiator were added. The introduction of nitrogen was continued and polymerization was allowed to proceed for 20 hours.
  • N,4-methacrylamidomethyl- 2,2- dimethyl l, 3 dioxolane a solution of 21.4 parts ofN,2 methacrylamidoethyl N,N dimethylaminoacetate betaine (prepared by hydrolysis of 26.5 parts of carhomethoxymethyl 2 methacryl'amidoethyl dimethyl ammonium chloride in 200 parts of water with dilute aqueous NaOH at pH 10 to 11 followed by neutralization with dilute aqueous hydrochloric acid to pH 7), 42.5 parts of methacrylarnide, and 0.10 part of initiator were added. The introduction of nitrogenwas continued and polymerization was allowed to proceed for 20 hours.
  • N,4-methacrylamidomethyl- 2,2- dimethyl l, 3 dioxolane a solution of 21.4 parts ofN,2 methacrylamidoethyl N,N dimethylaminoacetate betaine (prepared by hydrolysis of 26.5 parts of carhomethoxymethyl 2 methacryl'amidoeth
  • the copolymer solution was then adjusted to pH 1' to 2 for a period of about V2 hour and then neutralized to pH. 7, each as in Example I.
  • Excess acetone was added to the copolymer solution, which treatment caused coagulation of the copolymer.
  • This substance was then pulverized, and washed with acetone and dried to yield 86 parts of the white, water-soluble powder, namely, poly(N,2,3 dihydroxypropylmethacrylamide co N,2- methacrylamidoethyl N,N dimethylarninoacetate betaine co methacrylamide).
  • the relative viscosity of a 1% aqueous solution of this material at pH 7 and 30 C. was 1.86.
  • the copolymer solution was then adjusted topH l to 2 for a period of about V2 hour and then neutralized to pH 7, as set forth in Example 1.
  • Excess acetone was added to the copolymer solution, which treatment caused coagulation of the copolymer.
  • This substance was then pulverized, and washed with acetone and dried to yield 74 parts of the white, water-soluble powder, namely, poly(N,2,3 dihydroxypropylmethacrylamide co N,2 methacrylamidoethyl N,N dimethylaminoacetate betaine-co methacrylamide).
  • the relative viscosity of a 1% aqueous solution of this material at pH 7 and 30 C. was 1.92.
  • N,4-methacrylamidomethyl 2,2 dimethyl- 1,3' dioxolane a solution of 48-.4 parts of N,2 methacrylamidoethyl N,N diethylaminoacetate betaine (prepared by hydrolysis of 70.2 parts of carboethoxymethyl 2 methacrylamidoethyl diethylammonium bromide in 200 parts of water at pH 10 to 11 followed by neutralization to pH 7), 34.0 parts of methacrylamide, 7.1 parts of acrylamide, and 0.10 part of initiator were added. The introduction of nitrogen was continued and polymerization was allowed to proceed for 20 hours.
  • N,4-methacrylamidomethyl 2,2 dimethyl- 1,3' dioxolane a solution of 48-.4 parts of N,2 methacrylamidoethyl N,N diethylaminoacetate betaine (prepared by hydrolysis of 70.2 parts of carboethoxymethyl 2 methacrylamidoethyl diethylam
  • the copolymer solution was then adjusted to pH 1' to 2 for a period of about V2 hour and then neutralized to pH 7, as set forth in Example 1.
  • Excess acetone was added to the copolymer solution, which treatment caused coagulation of the copolymer.
  • This substance was then pulverized, and washed with acetone and dried to yield 107 parts of the white, water-soluble powder, namely, poly(N,2,3 dihydroxypropyhnethacrylamide co N,2 methacrylamidoethyl N,N diethylaminoacetate betaine co methacrylarnide co acrylamide).
  • N,3 methacrylamidopropyl N,N diethylaminoacetate betaine prepared by hydrolysis of 75.8 parts of carboethoxymethyl 3 methacrylamidopropyl diethylammonium' bromide in 200 parts of water at pH lO-to 11 followed by neutralization to pH 7
  • 42.5 parts of methacrylamide, and 0.10 part of initiator were added.
  • the introduction of nitrogen was continued and polymerization wasallowed to proceed for 20 hours.
  • the copolymer solution was then adjusted to pH 1 to 2 for a period of about V2 hour and then neutralized to pH 7, as set forth in Example I. Excess acetone was added to the copolymer solution, which treatment caused coagulation of the copolymer.
  • methyl-1,3-a'i0x0lane, N,2-methacrylamidoethyl-N,N- dim'ethyl-e-aminopropionate betaine, methacrylamide and acrylamz'de In a glass vessel there was placed 800 parts of water. The temperature was adjusted to 60 C., by means of a water bath, and nitrogen gas was passed through thewater for a period of about V2 hour to remove dissolved oxygen.
  • N,4-methacrylamidomethyl- 2,2-dimethyl-1,3-dioxolane a solution of 22.8 parts of N,2- methacrylamidoethyl-N,N- dimethyl-aaminopropionate betaine (prepared by hydrolysis of 37.0 parts of l-carbomethoxyethyl Z-methacrylamidoethyl dimethylammonium iodide in 200 parts of water at pH 10 to 11 followed by neutralization to pH 7, as set forth in Example. VI), 34.0. parts of. methacrylarnide, 14.2 parts of acrylamide,: and 010 part of initiator were added. The introduction of nitrogen was continued and poly- This substance was then pulverized,.
  • N,4-methacrylamidomethyl- 2,2-dimethyl-1,3-dioxolane a solution of 24.2 parts of N,3-methacrylamidopropyl-N,N-dimethyl-a-aminopropionate betaine (prepared by hydrolysis of 35.1 parts of 1- carboethoxyethyl-3-methacrylamidopropyl dimethylammonium bromide in 200 parts of water, at pH to 11 followed by neutralization to pH 7, as set forth in Example VI), 34.0 parts of methacrylamide, 9.9 parts of N,N-dimethylacrylarnide, and 0.10 part of initiator were added. The introduction of nitrogen was continued and polymerization was allowed to proceed for 20 hours.
  • the copolymer solution was then adjusted to pH 7. Excess acetone was added to the copolymer solution, which treatment caused coagulation of the copolymer. This substance was then pulverized, and washed with acetone and dried to yield 79 parts of the white, water-soluble powder, namely, poly(N,2,3-dihydroxypropylmethacrylamide co N,3-methacrylamidopropyl-N,N-dimethyl-aaminopropionate betaine co methacrylamide co N,N-dimethylacrylamide).
  • the relative viscosity of a 1% aqueous solution of this material at pH 7 and 30 C. was 2.03.
  • N,4-methacrylamidomethyl- 2,2-dimethyl-1,3-dioxolane a solution of 40.0 parts of N,2-acrylamidoethyl-N,N-dimethylaminoacetate betaine (prepared by hydrolysis of 59.0 parts of carbomethoxymethyl-Z-methacrylamidoethyl dimethylammonium bromide in 200 parts of water at pH 10 to 11 followed by neutralization to pH 7, each as in Example VI), 42.5 parts of methacrylamide, and 0.10 part of initiator were added. The introduction of nitrogen was continued and polymerization was allowed to proceed for 20 hours.
  • the copolymer solution was then adjusted to pH 1 to 2 for a period of about /2 hour and then neutralized to pH 7, as set forth in Example I. Excess acetone was added to the copolymer solution, which treatment caused coagulation of the copolymer. This substance was then pulverized, and washed with acetone and dried to yield 65 parts of the white, water-soluble powder, namely, poly(N,2,3-dihydroxypyropylmethacrylamide co N,2- acrylamidoethyl-N,N-dimethylaminoacetate betaine co methacrylamide). The relative viscosity of a 1% aqueous solution of this material at pH 7 and 30 C., was 2.09.
  • water-soluble powder namely, poly(N,2,3-dihydroxypropylrnethacrylamide co N,Z-acryIamidoethyI-N,N-dimethyl-a-aminopropionate betaine co methacrylamide).
  • N,4-methacrylarnidomethyl-Z,2-dimethyl-1,3-dioxolane a solution of 22.8 parts of N,3-acrylamidopropyl-N,N- dimethyl-a-aminopropionate betaine (prepared by hydrolysis of 37.0 parts of l-carbomethoxyethyl 3-acrylamidopropyl dimethylammonium iodide in 200 parts of water at pH 10 to 11 followed by neutralization to pH 7, as set forth in Example VI), 51.0 parts of methacrylamide, and I 0.10 part of initiator were added. The introduction of nitrogen was continued and polymerization was allowed to proceed for 20 hours.
  • N,4-methacrylarnidomethyl-Z,2-dimethyl-1,3-dioxolane a solution of 22.8 parts of N,3-acrylamidopropyl-N,N- dimethyl-a-aminopropionate betaine (prepared by hydrolysis of 37.0 parts of l-carbomethoxyeth
  • the copolymer solution was then adjusted to pH 1 to 2 for a period of about /2 hour and then neutralized to pH 7, as set forth in Example 1. Excess acetone was added to the copolymer solution to coagulate the copolymer, which was pulverized, washed with acetone and dried to yield 56 parts of the white, water-soluble powder, namely, poly(N,2,3-dihydroxypropylmethacrylamide co N,3-acrylamidopropyl-N,N-dimethyl-a-aminopropionate betaine co methacrylamide).
  • copolymer solution was then adjusted to pH 10 to 11 for a period of about /2 hour and then neutralized to pH 7, as set forth in Example VI. Excess acetone was added to. the copolymer solution to coagulate the copolymer which was pulverized, washed with acetone and dried to yield 58 parts of the white, water-soluble powder, namely,
  • N,2,3-dihydroxypropylmethacrylamide prepared by hydrolysis of 29.9 parts of N,4-methacrylamidomethyl2r,2rdimethyl-1,3-dioxolanev in parts of water at pH 1 to 2 followed by hydrolysis to pH 7, as set forth in Example V
  • 17.0 parts of methacrylamide, and 0.10 part of initiator were added.
  • the introduction of, nitrogen was continued and polymerization was allowed to proceed for 20 hours.
  • the copolymer solution wasthen adjusted to pH 10 to 11 for a period of about /2 hour and then neutralized to pH 7, as set forth in Example VI.
  • N,2 methacrylamidoethyl-N,N-dimethyl-fi-aminopropionate betaine a solution of 5.2 parts of N,2-methyl-1,3- dihydroxyisopropylmethacrylamide (prepared by hydrolysis of 6.4 parts of 2,2,5-trimethyl-N,S-methacrylamido- 1,3-dioxane in 20 parts of water at pH 1 to 2 followed by neutralization to pH 7, as set forth in Example V), 4.25 parts of methacrylamide, and 0.01 part of initiator were added. The introduction of nitrogen was continued and polymerization was allowed to proceed for 20 hours.
  • N,3 acrylamidopropyl N,N dimethyl-B-aminopropionate betaine a solution of 4.8 parts of N,2-methyl-1,3- dihydroxyisopropylacrylamide (prepared by hydrolysis of 6.0 parts of 2,2,5-trimethyl-N,5-acrylamido-1,3-dioxane in 20 parts of water at pH 1 to 2 followed by neutralization to pH 7, as set forth in Example V), 5.10 parts of methacrylamide, and 0.01 part of initiator were added. The introduction of nitrogen was continued and polymerization was allowed to proceed for 20 hours.
  • amides of general Formula VI there may be substituted other amides of general Formula VI.
  • suitable amides are acrylamide, ethacrylamide, propacrylamide, cyclohexacrylamide, N methylmethacrylamide, N,N-dimethylacrylamide, N-isopropylmethacrylamide, N-phenylmethacrylamide, N-methyl-N-ethylacrylamide, etc.
  • suitable ones are: benzoyl peroxide, tert'. butyl peroxide, tert. butyl hydroperoxide, acetyl peroxide, cumene hydroperoxide, hydrogen perox- 1'41 ide, sodium peroxide, sodium perborate, and sodium persulfate; ammonium persulfate-sodium bisfulfite, hydrogen peroxide-thiourea; and potassium persulfate-ferrous sulfate; and u,a'-azobis(isobutyronitrile) .u,ot'-aZObiS(u,'Y-dimethylvaleronitrile) oc,m'-aZ0biS u,'y,- -trimethylvaleronitrile) and a,a'-azobis(a-methylbutyronitrile)
  • the copolymers are: benzoyl peroxide, tert'. but
  • the gelling and de-gelling action is produced by virtue of the formation of complex compounds between borate ion and polyhydroxy compounds in which boron has a coordination number of 4. It is believed that the bridges, or cross-links, which are formed between borate ion and the new polymers in alkaline solutions may be represented as follows:
  • the coated layer quickly gels due to contact with the water-soluble boron compound.
  • the latter compoundv apparently migrates into the coated layer.
  • the aqueous solution of copolymer when containing light-sensitive silver halides and coated in like manner, quickly forms a gelled silver halide emulsion layer.
  • Suitable gelling agents for the sublayers include boric acid, sodium and potassium tetraborate, metaborate, and
  • dulbitol monoborate and diborates and, monoand polycondensation products and.their sodium andammonium salts set. forth in Examples 1 to. 19 of United States Patent 2,223,349 and in Examples 3, 4, 5, 7, 9, 14, and 18 to 35 of United States Patent 2,223,948.
  • An advantage of this invention is that it provides a new class of Water-permeable colloids which are useful as superior replacements for gelatin. Another advantage is that it provides new colloids which combine the advantageous properties of gelatin and polyvinyl alcohol, without the need for the temperature-controlled setting of, the former.
  • the copolymers moreover, are uniform in character and thus have advantages over gelatin.
  • a major, advantage resides in the fact that the co polymers can be gelled, de-gelled and re-gelled in a reversible and easily controllable fashion.
  • copolymers are soluble in water or water-alcohol mixtures, but are good colloid binding agents, and after the coated layers are set or gelled by means of borate gelling agents, they are strong, coherent and adherent to gelatin and other sublayers, such as those prepared by means of dispersions of poly(vinylidene chloride co acrylic acid esters co itaconic acid), or by means of mixed acetals of polyvinyl alcohol prepared from aldehydes containing acid groups (e. g., sodium o-sulfobenzaldehyde), together with other aldehydes, e.
  • aldehydes containing acid groups e. g., sodium o-sulfobenzaldehyde
  • the gelled layers are free from disadvantages of gelatin and gelatin-silver halide layers (i. e., non-uniformity and being subject to the deleterious action of molds and bacteria). Still other advantages will be apparent to those skilled in the art.
  • R, R" and R' are members taken from the group consisting of hydrogen, alkyl of l to 3 carbon atoms, phenyl and cyclohexyl, R is a saturated bivalent aliphatic hydrocarbon radical of 2 to 6 carbon atoms, R and R are alkyl radicals of 1 to 3 carbon atoms, R is a saturated bivalent aliphatic hydrocarbon radical containing 1 to 4 carbon atoms, Q and Q" are members taken from the group consisting of hydrogen and alkyl radicals of 1 through 3 carbon atoms, m is a number taken from the group consisting of O, l, 2, 3, and 4, and n is a number taken from the group consisting of and l and the sum of m and n is at least 1, wherein said first unit comprises 5 to 60 mole percent, the second 5 to 60 mole percent and the third 30 to 90 mole percent of the copolymer.
  • R, R and R' are members taken from the group consisting of hydrogen, alkyl of'l to 3 carbon atoms, phenyl and cyclohexyl,,R ,is a saturated bivalent aliphatic hydrocarbon radical of 2 to 6 carbon atoms, R and R are alkyl radicals of 1 to 3 carbon atoms, R is a saturated bivalent aliphatic hydrocarbon radical containing 1 to 4'carbon atoms, Q andQ" are members taken from the group consisting of hydrogen and alkyl radicals of ,1 through 3' carbon atoms, m is a number taken from the groupconsisting of 0, 1, 2, 3, and 4, and n is a number taken. from the group consisting of 0 and 1 and the sum of m and'n is at least 1', wherein said first unit comprises 5 to 60 mole percent, the second 5 to 60 mole percent and the third 30 to mole percent of the copolymer.
  • R is a member taken from the group consisting of hydrogen, alkyl of l to 3 carbon atoms, phenyl and cyclohexyl
  • Q' and Q" are members taken from the group consisting of hydrogen and alkyl radicals of 1 through 3 carbon atoms
  • m is a member taken from the group consisting of 0, 1, 2, 3, and 4
  • n is a number taken from the group consisting of and 1 and the sum of m and n is at least 1, and (b) their acetals of low molecular weight from ketaldones of 1 to 7 carbon atoms from to 60 mole percent of
  • (2) an ethylenically unsaturated amide taken from the group consisting of (a) those of the general formula:
  • R is a saturated bivalent aliphatic hydrocarbon radical of 2 to 6 carbon atoms
  • R and R are alkyl radicals of 1 to 3 carbon atoms
  • R and R are members taken from the group consisting of hydrogen, methyl and ethyl
  • Q and Q" are members taken from the group consisting of hydrogen and alkyl radicals of 1 through 3 carbon atoms
  • m is a number taken from the group consisting of 0, 1, 2, 3, and 4
  • n is a number taken from the group consisting of 0 and l and the sum of m and n is at least 1; said first compound being present in an amount of 5 to mole percent, the second in an amount of 5 to 60 mole percent and the third in an amount of 30 to 60 mole percent.

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US415161A 1954-03-09 1954-03-09 Terpolymers of nu-acrylamidoalkyl betaines Expired - Lifetime US2846417A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
NL87296D NL87296C (instruction) 1954-03-09
BE535582D BE535582A (instruction) 1954-03-09
US415161A US2846417A (en) 1954-03-09 1954-03-09 Terpolymers of nu-acrylamidoalkyl betaines
GB32913/54A GB786345A (en) 1954-03-09 1954-11-12 Improvements in or relating to copolymers
FR1122084D FR1122084A (fr) 1954-03-09 1955-02-09 Perfectionnements relatifs aux copolymères
DEP13535A DE1046318B (de) 1954-03-09 1955-02-09 Verfahren zur Herstellung von Additions-Mischpolymeren

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BE (1) BE535582A (instruction)
DE (1) DE1046318B (instruction)
FR (1) FR1122084A (instruction)
GB (1) GB786345A (instruction)
NL (1) NL87296C (instruction)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5512644A (en) * 1993-09-08 1996-04-30 Toyo Boseki Kabushiki Kaisha Ampholytic polymer capable of absorbing aqueous electrolyte solution

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DE1290042B (de) * 1963-10-24 1969-02-27 Eastman Kodak Co Photographische Gelatine-Silberhalogenidemulsion
US5418217A (en) * 1990-04-14 1995-05-23 Union Oil Company Of California Composition for selectively reducing subterranean formation permeability
US5225090A (en) * 1991-03-27 1993-07-06 Union Oil Company Of California Visible gels prepared using stainless steel as a crosslinking agent

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US2508718A (en) * 1945-10-16 1950-05-23 Gen Aniline & Film Corp Preparation of amphoteric amides of acrylic acid and their polymers
US2533166A (en) * 1945-10-16 1950-12-05 Gen Aniline & Film Corp Process for polymerizing watersoluble polyacrylamides and poly-alpha-substituted acrylamides

Non-Patent Citations (1)

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Title
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5512644A (en) * 1993-09-08 1996-04-30 Toyo Boseki Kabushiki Kaisha Ampholytic polymer capable of absorbing aqueous electrolyte solution

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GB786345A (en) 1957-11-13
NL87296C (instruction)
FR1122084A (fr) 1956-08-31
DE1046318B (de) 1958-12-11
BE535582A (instruction)

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